Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated

Definitions

• the invention relates to coated particles of an alkaline earth metal carbonate, preferably CaCO 3 , which are at least partially coated with at least one coating agent and have a specific surface of more than 50 m 2 g -1 before coating.
• the invention also relates to the production of such particles and their use.
• Calcium carbonate is used as a filler material in paintings, rubber, paper, pharmacy, plastics and so on. Such calcium carbonate is obtained from natural deposits, thereafter being finely ground, or is obtained via chemical precipitation and drying of the precipitate. It is also known that the dispersibility of fillers in a polymeric matrix widely varies, depending upon the particle size of the filler, and characteristically decreases with diminishing particle sizes; thus, to utilize very finely divided particulates in polymeric matrices, it is necessary to extend the mixing times or the shearing effectiveness of the mixer. This is counterproductive when heat-sensitive polymers are used, because any improvement in the mechanical properties due to the filler content is lost because of concomitant thermal degradation of the polymer.
• yet another category of process features the treatment of a calcareous filler to improve its wettability by means of hydrocarbons and plastic materials by contacting the same with alkylarylsulfonic acids or salts, the calcium salt thereof being essentially insoluble in water, in an amount at least equal to that required to form a monomolecular layer or a coating covering the entire surface of the particles or grains, as described in FR-A 2 138 300.
• This publication specifically relates to calcium carbonate powders having a low specific surface, on the order of 0.5 to 3 m 2 /g (BET method).
• FR-A 2 480 771 discloses the treatment of calcium carbonate powder with an organic sulfonic acid or salt thereof, together with a fatty acid compound. The beginning calcium carbonate has a specific surface, measured by the BET method, between 50 m 2 /g and 0.2 m 2 /g.
• Plastisols are dispersions of polymers, often comprising polyvinyl chloride (PVC) in organic solvents having high boiling points and usually containing softeners and stabilizers. Plastisols are useful e.g. for coating metals and other substrates, such as underbody sealants for automobiles, for preparing artificial leather, etc.
• PVC polyvinyl chloride
• Polyvinyl chloride plastisols offer several advantages for use as sealant compositions : a good balance of strength, elongation and toughness, minimal to no volatile organic component and low cost.
• a plastisol When a plastisol is intended for application by means of a spray gun, it should adhere to the substrate and form a smooth film thereon. Flowing and any movement of the film due to gravitational forces should be suppressed as long as the plastisol is liquid or pasty, i.e. before it is cured. This kind of adhesion can be achieved by modifying the rheological properties of the plastisol.
• a good plastisol When being applied to a substrate by means of a spray gun, a good plastisol should exhibit a high viscosity when the shearing force is low and a low viscosity when the shearing force is high. Furthermore, it should be characterized by a high yield stress and good thixotropic properties.
• the filler material should be suitable for plastisols which may be applied by a spray gun, i.e. a plastisol containing said filler material should have a high yield stress, it should exhibit a high viscosity when the shearing force is low and a low viscosity when the shearing force is high. Furthermore, these properties should be constant for a certain period of time.
• Plastisols containing the particles according to the present invention show excellent rheological properties, particularly high yield stress values, good viscosities and thixotropy.
• the particles according to the invention have a specific surface of more than 50 m 2 g -1 before coating, preferably more than or equal to 55 m 2 /g, still more preferably above or equal to 60 m 2 /g and most preferably above or equal to 65 m 2 /g before coating. Values of the specific surface of the particles before coating higher than or equal to 70 m 2 /g, specifically higher than or equal to 75 m 2 /g and more specifically higher than or equal to 80 m 2 /g are particularly convenient.
• the particles have usually a specific surface lower than or equal to 300 m 2 g -1 , more preferably lower than or equal to 180 m 2 g -1 and most preferably lower than or equal to 105 m 2 g -1 before coating.
• Such particles of precipitated calcium carbonate are known in the prior art and may be prepared by precipitating calcium carbonate particles from a suspension of Ca(OH) 2 in the presence of an agent such as citric acid, polyacrylic acid, sodium dioctylsulfosuccinate and polyaspartic acid.
• an agent such as citric acid, polyacrylic acid, sodium dioctylsulfosuccinate and polyaspartic acid.
• an agent such as citric acid, polyacrylic acid, sodium dioctylsulfosuccinate and polyaspartic acid.
• the specific surface of a precipitated calcium carbonate particle before coating is defined as the surface area which is determined according to the BET-method (adsorption isotherm of nitrogen according to Brunnauer-Emmett-Teller (BET)).
• BET Brunnauer-Emmett-Teller
• the surface of a powder can be calculated from the N 2 -isotherm, which is observed at the boiling point of liquid nitrogen. For details, it can be referred to the ISO 9277 norm (1995-05-15).
• the particles of an alkaline earth metal carbonate is calcium carbonate or magnesium carbonate, calcium carbonate being particularly preferred.
• the particles according to the invention are coated with a coating agent.
• a coating agent Several coating agents are suitable for that purpose.
• the coating agent comprises at least a compound selected from the group consisting of organic sulfonic acids; alkylsulfates; fatty acids, optionally substituted with a hydroxy group (i.e. hydroxy fatty acids); and the salts thereof.
• organic sulfonic acids encompasses any compound bearing at least one group -SO 3 H or a salt thereof and at least 1 carbon atom.
• organic sulfonic acids may contain further functional groups, such as esters.
• organic sulfonic acids encompass alkylsulfosuccinates such as dioctylsulfosuccinate and its sodium salt.
• alkyl denotes, if not otherwise specified, linear or branched alkyl chains, preferably having 1 to 30, more preferably 1 to 18, most preferably 1 to 12 and in particular 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, n-undecyl, i-undecyl, n-dodecyl, i-dodecyl and the like.
• the coating agent comprises at least a fatty acid, optionally substituted with a hydroxy group.
• Suitable fatty acids are linear or branched aliphatic carboxylic acids, preferably having 8 to 22 carbon atoms, more preferably 12 to 18 and in particular 16 to 18 carbon atoms, and the salts thereof.
• the aliphatic chains of the fatty acids may be saturated or unsaturated. Saturated aliphatic fatty acids are preferred.
• the coating agent comprises stearic acid or its salts. When the coating agent comprises a hydroxy fatty acid or a salt thereof, hydroxy stearic acid is preferred. Most preferably, the stearic acid bears the hydroxy group in 12-position (CH 3 -(CH 2 ) 4 -CH 2 -CHOH-CH 2 -(CH 2 ) 8 -CH 2 - COOH).
• the precipitated calcium carbonate particles having a specific surface of more than 50 m 2 g -1 before coating are directly treated, either with the fatty acids or hydroxy fatty acids themselves, or with the alkali metal or ammonium salts thereof.
• aqueous solutions or suspensions of a salt of the fatty acid or hydroxy fatty acid are utilized as the means for effecting the subject surface treatment.
• the coating agent comprises at least a sulfur organic compound.
• the coating agent comprises a compound selected from the group consisting of alkylsulfonic acids, arylsulfonic acids, alkylarylsulfonic acids, alkylsulfosuccinates, alkylsulfates and the salts thereof.
• aryl denotes an aromatic mono- or bicyclic hydrocarbon comprising 6 to 10 carbon atoms, such as phenyl and naphthyl, optionally substituted with halogen.
• alkylaryl denotes an "alkyl” residue as defined above covalently linked to an "aryl"-residue as defined above, such as -CH 2 C 6 H 5 , -CH 2 CH 2 C 6 H 5 , -CH 2 CH 2 CH 2 C 6 H 5 , and the like.
• the coating agent comprises a compound represented by general formula (I-A) or (I-B) wherein R 1 , R 7 , R 9 and R 10 are independently a single bond, -O-, -C 1 -C 18 -alkylene- or - C 2 -C 18 -alkenylene- (wherein in the alkylene- or in the alkenylene-chain optionally 1, 2 or 3 -CH 2 - groups may be replaced by -O-); R 2 , R 3 , R 4 , R 5 and R 6 are independently -H, -C 1 -C 18 -alkyl (wherein in the alkyl-chain optionally 1, 2 or 3 -CH 2 - groups may be replaced by -O-), -OH, -F, -Cl, -CN, -CO 2 H, -CO-C 1 -C 6 -alkyl, -CO 2 -C 1 -C 6 -alkyl, -O-CO-
• alkylene denotes bivalent linear or branched alkylene chains, such as -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH(CH 3 )-, -CH 2 CH(CH 3 )-, -CH 2 CH 2 CH(CH 3 )-, -CH 2 CH(CH 3 )CH 2 -, and the like.
• R 1 , R 7 , R 9 and R 10 are independently a single bond or -C 1 -C 6 -alkylene- (wherein in the alkylene-chain optionally 1 or 2 -CH 2 - groups may be replaced by -O-);
• R 2 , R 3 , R 4 , R 5 and R 6 are independently -H or -C 1 -C 18 -alkyl (wherein in the alkyl-chain optionally 1, 2 or 3 -CH 2 - groups may be replaced by -O-);
• R 8 is -H or -C 1 -C 6 -alkyl; and
• R 11 and R 12 are independently -C 1 -C 12 -alkyl (wherein in the alkyl-chain optionally 1, 2 or 3 -CH 2 - groups may be replaced by -O-).
• R 1 and R 7 are a single bond;
• R 2 , R 3 R 5 and R 6 are -H
• R 4 is -H or -C 1 -C 6 -alkyl;
• R 8 is -H;
• R 9 and R 10 are independently a single bond or -CH 2 -;
• R 11 and R 12 are independently -C 1 -C 12 -alkoxy.
• alkoxy denotes an "alkyl” residue as defined above covalently linked to an oxygen atom, such as -OCH 3 , -OCH 2 CH 3 , and the like.
• the coating agent comprises one or more compounds selected from the group consisting of benzene sulfonic acid, toluene sulfonic acid, dioctylsulfosuccinate and the salts thereof.
• the coating agent comprises a compound of formula (I-A), wherein R 1 is a single bond; R 2 , R 3 , R 5 and R 6 are -H; and R 4 is -H or -C 1 -C 10 -alkyl, preferably -H or -C 1 -C 6 -alkyl; coated particles exhibiting excellent properties may also be obtained with precipitated calcium carbonate having a specific surface of 50 m 2 g -1 or below 50 m 2 g -1 before coating.
• the coating agent comprises benzene sulfonic acid or toluene sulfonic acid.
• the specific surface of the calcium carbonate particles is preferably within the range of from 25 to 50 m 2 g -1 , more preferably from 30 to 50 m 2 g -1 , most preferably from 35 to 50 m 2 g -1 and in particular from 40 to 50 m 2 g -1 before coating.
• the specific surface may also be above 50 m 2 g -1 before coating, more preferably above or equal to 55 m 2 /g, still more preferably above or equal to 60 m 2 /g and most preferably above or equal to 65 m 2 /g before coating.
• Values of the specific surface of the particles before coating higher than or equal to 70 m 2 /g, specifically higher than or equal to 75 m 2 /g and more specifically higher than or equal to 80 m 2 /g are particularly convenient, as described supra.
• the particles according to invention have an average primary particle size within the range of from 0.1 to 30 nm.
• the primary particle size relates to the coated particles and the condition in which substantially no agglomerates are formed.
• the primary particle size may be determined according to the method described in NF 11601 / 11602 NF.
• the average primary particle size is within the range of from 1 to 30 nm.
• the present invention also relates to compositions comprising the coated particles described above and a polymer.
• the polymer comprises polyvinyl chloride.
• the polymer has an weight average molecular weight M w within the range of from 5,000 to 500,000 gmol -1 , more preferably 10,000 to 400,000 gmol -1 , most preferably 25,000 to 250,000 gmol -1 .
• the compositions according to the invention contain
• compositions according to the invention are summarized here below : Table 1 : [wt.-%] preferably more preferably most preferably coated particles 1-50 5-30 15-25 polymer 5-75 15-50 25-35 plasticizer 10-60 20-50 30-40 Solvent 0.5-15 1-10 3-6 filler 0-30 0-20 0-16 promoter 0-20 0-10 1-6 desiccant 0-20 0-10 1-2 further additives 0-15 0-10 0-5
• the present invention also relates to a process for the preparation of coated particles as described above comprising the step of contacting uncoated particles of an alkaline earth metal carbonate having a specific surface of more than 50 m 2 g -1 with a coating agent.
• the coating agent comprises one or more of the preferred compounds as described above.
• the process comprises the steps of
• the present invention also relates to the use of the coated particles as described above as filler in polymeric compositions.
• Particles of calcium carbonate having a specific surface ranging from 41 to 104 m 2 g -1 (before coating) were obtained according to the method described in WO 03/004414.
• These precipitated calcium carbonate particles were coated with a coating agent selected from Marlon, AOT, stearic acid and hydroxystearine.
• Marlon is a mixture comprising 85 wt.-% benzenesulfonic acid and 15 wt.-% toluenesulfonic acid sodium salt and "AOT” means dioctylsulfosuccinate sodium salt.
• AOT means dioctylsulfosuccinate sodium salt.
• the properties of the particles are summarized in Table 2 here below and are compared with ultrafine precipitated calcium carbonate coated with stearine (a mixture of saturated and unsaturated branched aliphatic carboxylic acids e.g. Priplus, Edenor, Pristerene, Undesa, Prifrac, Radiacid, Safacid, Cremer) as coating agent and having a specific surface of 20 m 2 g -1 before coating.
• stearine a mixture of saturated and unsaturated branched aliphatic carboxylic acids e.g. Priplus, Edenor, Pristerene, Undesa, Prifrac, Radiacid, Safacid, Cremer
• Table 2 particle specific surface (before coating) coating agent Reference 20 m 2 g -1 stearin type-1 41 m 2 g -1 Marlon type-2 66 m 2 g -1 Marlon type-3 70 m 2 g -1 Marlon type-4 85 m 2 g -1 Marlon type-5 70 m 2 g -1 AOT type-6 70 m 2 g -1 AOT type-7 85 m 2 g -1 AOT type-8 53 m 2 g -1 stearin type-9 77 m 2 g -1 stearin type-10 104 m 2 g -1 stearin type-11 70 m 2 g -1 hydroxystearin type-12 70 m 2 g -1 hydroxystearin
• Table 3 Two different formulations were prepared containing polyvinyl chloride and the coated calcium carbonate particles of Example 1.
• the composition of said formulations is summarized in Table 3 here below.
• Table 3 formulation A [g] B [g] Plasticizer 114.7 105 Polymer 90.1 75 Solvent 13.8 12 Filler 0.3 50,1 Other additives 0.3 0,9 Batch ⁇ 219.2 243.0 coated precipitated calcium carbonate • 100% 73.5 48.0 • 75% 55.1 36.0 • 65% 47.8 31.2 • 50% 36.8 24.0 Promoter 4.0 3.0 Desiccant 3.3 6.0
• the rheological properties of the various formulations obtained from Example 2 were investigated according to the ISO 3219 norm. The measurements were performed in a rheometer type UDS 200 equipped with a mobile DIN 125 conical cylinder. This rheometer measures the development of the shearing forces and the viscosity in function of the velocity gradient imposed. All measurements were performed at 25° C according to the following procedure:
• the content of the coated precipitated calcium carbonate particles in the formulations was varied (100 %, 75 %, 65 % and 50%).
• Table 4 formulation A coating with Marlon yield stress [Pa] viscosity [Pa s] thixotropy [Pa s -1 ] Reference 100% 174 3.3 1719 type-1 (41 m 2 g -1 ) after 1 day 100% 243 4.5 3720 75% 427 6.5 16291 65% 90 2.2 1300 50% 29 1.2 941
• Table7 formulation B coating with Marlon yield stress [Pa] viscosity [Pa s] thixotropy [Pa s -1 ] Reference 100% 153 3.7 4543 type-4 (85 m 2 g -1 ) after 1 day 100% 206 5.8 11610 75% 89 3.1 7236 65% 100 2.7 4907 50% 37 1.9 4634
• Table 11 formulation B coating with stearin yield stress [Pa] viscosity [Pa s] thixotropy

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paints Or Removers (AREA)

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